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Lithium nitride

Lithium nitride
Unit cell ball and stick model of lithium nitride
__ Li+ __ N3−
Structure Li3N.svg
Crystal structure of lithium nitride.
Names
Preferred IUPAC name
Lithium nitride
Other names
Trilithium nitride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.043.144 Edit this at Wikidata
EC Number
  • 247-475-2
Gmelin Reference
 1156
CompTox Dashboard (EPA)
Properties
Chemical formula
 Li3N
Molar mass 34.83 g/mol
Appearance red, purple solid
Density 1.270 g/cm3
Melting point 813 °C (1,495 °F; 1,086 K)
reacts
log P 3.24
Structure
Crystal structure
 see text
Hazards
Main hazards reacts with water to release ammonia
GHS pictograms GHS02: FlammableGHS05: Corrosive
GHS Signal word Danger
GHS hazard statements
 H260, H314, H318
GHS precautionary statements
 P223, P231+232, P260, P264, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P335+334, P363, P370+378, P402+404, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
0
2
Related compounds
Other anions
 Lithium oxide
Other cations
 Sodium nitride
Related compounds
 Lithium amide Lithium imide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Lithium nitride is a compound with the formula Li3N. It is the only stable alkali metal nitride. The solid has a reddish-pink color and high melting point.[1]

Preparation and handling

Lithium nitride is prepared by direct combination of elemental lithium with nitrogen gas:[2]

6 Li + N2 → 2 Li3N

Instead of burning lithium metal in an atmosphere of nitrogen, a solution of lithium in liquid sodium metal can be treated with N2. Lithium nitride reacts violently with water to produce ammonia:

Li3N + 3 H2O → 3 LiOH + NH3

Structure and properties

alpha-Li3N (stable at room temperature and pressure) has an unusual crystal structure that consists of two types of layers, one sheet has the composition Li2N− contains 6-coordinate N centers and the other sheet consists only of lithium cations.[3] Two other forms are known: beta-Lithium nitride, formed from the alpha phase at 4,200 bars (4,100 atm) has the sodium arsenide (Na3As) structure; gamma-Lithium nitride (same structure as Li3Bi) forms from the beta form at 35 to 45 gigapascals (350,000 to 440,000 atm).[4]

Lithium nitride shows ionic conductivity for Li+, with a value of c. 2×10−4Ω−1cm−1, and an (intracrystal) activation energy of c. 0.26eV (c. 24 kJ/mol). Hydrogen doping increases conductivity, whilst doping with metal ions (Al, Cu, Mg) reduces it.[5][6] The activation energy for lithium transfer across lithium nitride crystals (intercrystalline) has been determined to be higher at c. 68.5 kJ/mol.[7] The alpha form is a semiconductor with band gap of c. 2.1 eV.[4]

Reaction with hydrogen at under 300 °C (0.5 MPa pressure) produces lithium hydride and lithium amide.[8]

Lithium nitride has been investigated as a storage medium for hydrogen gas, as the reaction is reversible at 270 °C. Up to 11.5% by weight absorption of hydrogen has been achieved.[9]

Reacting lithium nitride with carbon dioxide results in amorphous carbon nitride (C3N4), a semiconductor, and lithium cyanamide (Li2CN2), a precursor to fertilizers, in an exothermic reaction.[10] [11]

References

  1. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  2. ^ E. Döneges "Lithium Nitride" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, New York. Vol. 1. p. 984.
  3. ^ Barker M. G.; Blake A. J.; Edwards P. P.; Gregory D. H.; Hamor T. A.; Siddons D. J.; Smith S. E. (1999). "Novel layered lithium nitridonickelates; effect of Li vacancy concentration on N co-ordination geometry and Ni oxidation state". Chemical Communications (13): 1187–1188. doi:10.1039/a902962a.
  4. ^ a b Walker, G, ed. (2008). Solid-State Hydrogen Storage: Materials and Chemistry. §16.2.1 Lithium nitride and hydrogen:a historical perspective.
  5. ^ Lapp, Torben; Skaarup, Steen; Hooper, Alan (October 1983). "Ionic conductivity of pure and doped Li3N". Solid State Ionics. 11 (2): 97–103. doi:10.1016/0167-2738(83)90045-0.
  6. ^ Boukamp, B. A.; Huggins, R. A. (6 September 1976). "Lithium ion conductivity in lithium nitride". Physics Letters A. 58 (4): 231–233. doi:10.1016/0375-9601(76)90082-7.
  7. ^ Boukamp, B. A.; Huggins, R. A. (January 1978). "Fast ionic conductivity in lithium nitride". Materials Research Bulletin. 13 (1): 23–32. doi:10.1016/0025-5408(78)90023-5.
  8. ^ Goshome, Kiyotaka; Miyaoka, Hiroki; Yamamoto, Hikaru; Ichikawa, Tomoyuki; Ichikawa, Takayuki; Kojima, Yoshitsugu (2015). "Ammonia Synthesis via Non-Equilibrium Reaction of Lithium Nitride in Hydrogen Flow Condition". Materials Transactions. 56 (3): 410–414. doi:10.2320/matertrans.M2014382.
  9. ^ Ping Chen; Zhitao Xiong; Jizhong Luo; Jianyi Lin; Kuang Lee Tan (2002). "Interaction of hydrogen with metal nitrides and amides". Nature. 420 (6913): 302–304. doi:10.1038/nature01210. PMID 12447436.
  10. ^ Yun Hang Hu, Yan Huo (12 September 2011). "Fast and Exothermic Reaction of CO2 and Li3N into C–N-Containing Solid Materials". The Journal of Physical Chemistry A. The Journal of Physical Chemistry A 115 (42), 11678-11681. 115 (42): 11678–11681. doi:10.1021/jp205499e.
  11. ^ Darren Quick (21 May 2012). "Chemical reaction eats up CO2 to produce energy...and other useful stuff". NewAtlas.com. Retrieved 17 April 2019.

See also

Salts and covalent derivatives of the nitride ion
NH3
N2H4 		He(N2)11
Li3N Be3N2 BN β-C3N4
g-C3N4
CxNy 		N2 NxOy NF3 Ne
Na3N Mg3N2 AlN Si3N4 PN
P3N5 		SxNy
SN
S4N4 		NCl3 Ar
K Ca3N2 ScN TiN VN CrN
Cr2N 		MnxNy FexNy CoN Ni3N CuN Zn3N2 GaN Ge3N4 As Se NBr3 Kr
Rb Sr3N2 YN ZrN NbN β-Mo2N Tc Ru Rh PdN Ag3N CdN InN Sn Sb Te NI3 Xe
Cs Ba3N2 Hf3N4 TaN WN Re Os Ir Pt Au Hg3N2 TlN Pb BiN Po At Rn
Fr Ra3N2 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La CeN Pr Nd Pm Sm Eu GdN Tb Dy Ho Er Tm Yb Lu
Ac Th Pa UN Np Pu Am Cm Bk Cf Es Fm Md No Lr


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